Skip to main content
SpringerLink
Log in

Enhancement of the hydrogen evolution performance by finely tuning the morphology of Co-based catalyst without changing chemical composition

  • Research Article
  • Published:
Nano Research Aims and scope Submit manuscript

Abstract

Transition-metal phosphides, as the promising alternatives to noble metal catalysts, have been widely used as efficient electrocatalysts for hydrogen evolution reaction (HER). In this work, three kinds of cobalt-8-hydroxyquinoline (Coqx) with different size and nanostructures are synthesized by varying the hydrothermal conditions, which was named as Coqx-L, Coqx-M and Coqx-S according to the decreased size. Accordingly, the CoxP/NC with three different size nanostructures (CoxP/NC-L, CoxP/NC-M and CoxP/NC-S) are obtained by the sequential carbonization and phosphidation of Coqx. The X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) results imply the identical chemical composition in these catalysts with different morphologies. Thus, systematic study is carried out to reveal the relationship between catalytic performance and morphologies of materials with the same chemical composition. The experimental result indicates that the morphology of CoxP/NC plays a crucial role on the surface area and electron transfer. Finally, the catalyst of CoxP/NC-S with the smallest size nanostructrue exhibits the best HER performance with a low overpotential at current density of 10 mA/cm2 (η = 56.9 and 115.6 mV) and a small Tafel slope (52.3 and 69.3 mV/dec) in both 0.1 M HClO4 and 1.0 M KOH as well as long-term stability.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Similar content being viewed by others

References

  1. Habas, S. E.; Platt, H. A. S.; Van Hest, M. F. A. M.; Ginley, D. S. Low-cost inorganic solar cells: From ink to printed device. Chem. Rev. 2010, 110, 6571–6594.

    Article  Google Scholar 

  2. Cabán-Acevedo, M.; Stone, M. L.; Schmidt, J. R.; Thomas, J. G.; Ding, Q.; Chang, H. C.; Tsai, M. L.; He, J. H.; Jin, S. Efficient hydrogen evolution catalysis using ternary pyrite-type cobalt phosphosulphide. Nat. Mater. 2015, 14, 1245–1251.

    Article  Google Scholar 

  3. Qiu, H. J.; Ito, Y.; Cong, W. T.; Tan, Y. W.; Liu, P.; Hirata, A.; Fujita, T.; Tang, Z.; Chen, M. W. Nanoporous graphene with single-atom nickel dopants: An efficient and stable catalyst for electrochemical hydrogen production. Angew. Chem., Int. Ed. 2015, 54, 14031–14035.

    Article  Google Scholar 

  4. Geng, X. M.; Sun, W. W.; Wu, W.; Chen, B. J. M.; Al-Hilo, A.; Benamara, M.; Zhu, H. L.; Watanabe, F.; Cui, J. B.; Chen, T. P. Pure and stable metallic phase molybdenum disulfide nanosheets for hydrogen evolution reaction. Nat. Commun. 2016, 7, 10672.

    Article  Google Scholar 

  5. Turner, J. A. Sustainable hydrogen production. Science 2004, 305, 972–974.

    Article  Google Scholar 

  6. Wu, Y. Y.; Li, G. D.; Liu, Y. P.; Yang, L.; Lian, X. R.; Asefa, T.; Zou, X. X. Overall water splitting catalyzed efficiently by an ultrathin nanosheet-built, hollow Ni3S2-based electrocatalyst. Adv. Funct. Mater. 2016, 26, 4839–4847.

    Article  Google Scholar 

  7. Zheng, Y.; Jiao, Y.; Jaroniec, M.; Qiao, S. Z. Advancing the electrochemistry of the hydrogen-evolution reaction through combining experiment and theory. Angew. Chem., Int. Ed. 2015, 54, 52–65.

    Article  Google Scholar 

  8. Parkinson, G. S.; Novotný, Z.; Jacobson, P.; Schmid, M.; Diebold, U. Room temperature water splitting at the surface of magnetite. J. Am. Chem. Soc. 2011, 133, 12650–12655.

    Article  Google Scholar 

  9. Cook, T. R.; Dogutan, D. K.; Reece, S. Y.; Surendranath, Y.; Teets, T. S.; Nocera, D. G. Solar energy supply and storage for the legacy and nonlegacy worlds. Chem. Rev. 2010, 110, 6474–6502.

    Article  Google Scholar 

  10. Bai, S.; Wang, C. M.; Deng, M. S.; Gong, M.; Bai, Y.; Jiang, J.; Xiong, Y. J. Surface polarization matters: Enhancing the hydrogen-evolution reaction by shrinking Pt shells in Pt-Pd-graphene stack structures. Angew. Chem., Int. Ed. 2014, 53, 12120–12124.

    Article  Google Scholar 

  11. Anantharaj, S.; Karthik, P. E.; Subramanian, B.; Kundu, S. Pt nanoparticle anchored molecular self-assemblies of DNA: An extremely stable and efficient HER electrocatalyst with ultralow Pt content. ACS Catal. 2016, 6, 4660–4672.

    Article  Google Scholar 

  12. Voiry, D.; Yamaguchi, H.; Li, J. W.; Silva, R.; Alves, D. C. B.; Fujita, T.; Chen, M. W.; Asefa, T.; Shenoy, V. B.; Eda, G. et al. Enhanced catalytic activity in strained chemically exfoliated WS2 nanosheets for hydrogen evolution. Nat. Mater. 2013, 12, 850–855.

    Article  Google Scholar 

  13. Wu, Z. X.; Guo, J. P.; Wang, J.; Liu, R.; Xiao, W. P.; Xuan, C. J.; Xia, K. D.; Wang, D. L. Hierarchically porous electrocatalyst with vertically aligned defect-rich CoMoS nanosheets for the hydrogen evolution reaction in an alkaline medium. ACS Appl. Mater. Interfaces 2017, 9, 5288–5294.

    Article  Google Scholar 

  14. Wang, J. H.; Cui, W.; Liu, Q.; Xing, Z. C.; Asiri, A. M.; Sun, X. P. Recent progress in cobalt-based heterogeneous catalysts for electrochemical water splitting. Adv. Mater. 2016, 28, 215–230.

    Article  Google Scholar 

  15. Wan, J.; Yao, X.; Gao, X.; Xiao, X.; Li, T. Q.; Wu, J. B.; Sun, W. M.; Hu, Z. M.; Yu, H. M.; Huang, L. et al. Microwave combustion for modification of transition metal oxides. Adv. Funct. Mater. 2016, 26, 7263–7270.

    Article  Google Scholar 

  16. Cao, B. F.; Veith, G. M.; Neuefeind, J. C.; Adzic, R. R.; Khalifah, P. G. Mixed close-packed cobalt molybdenum nitrides as non-noble metal electrocatalysts for the hydrogen evolution reaction. J. Am. Chem. Soc. 2013, 135, 19186–19192.

    Article  Google Scholar 

  17. Zhang, Y. Q.; Ouyang, B.; Xu, J.; Jia, G. C.; Chen, S.; Rawat, R. S.; Fan, H. J. Rapid synthesis of cobalt nitride nanowires: Highly efficient and low-cost catalysts for oxygen evolution. Angew. Chem., Int. Ed. 2016, 55, 8670–8674.

    Article  Google Scholar 

  18. Popczun, E. J.; Read, C. G.; Roske, C. W.; Lewis, N. S.; Schaak, R. E. Highly active electrocatalysis of the hydrogen evolution reaction by cobalt phosphide nanoparticles. Angew. Chem., Int. Ed. 2014, 53, 5427–5430.

    Article  Google Scholar 

  19. Tabassum, H.; Guo, W. H.; Meng, W.; Mahmood, A.; Zhao, R.; Wang, Q. F.; Zou, R. Q. Metal-organic frameworks derived cobalt phosphide architecture encapsulated into B/N co-doped graphene nanotubes for all pH value electrochemical hydrogen evolution. Adv. Energy Mater. 2017, 7, 1601671.

    Article  Google Scholar 

  20. Xiao, P.; Chen, W.; Wang, X. A review of phosphide-based materials for electrocatalytic hydrogen evolution. Adv. Energy Mater. 2015, 5, 1500985.

    Article  Google Scholar 

  21. Feng, J. X.; Xu, H.; Dong, Y. T.; Lu, X. F.; Tong, Y. X.; Li, G. R. Efficient hydrogen evolution electrocatalysis using cobalt nanotubes decorated with titanium dioxide nanodots. Angew. Chem., Int. Ed. 2017, 56, 2960–2964.

    Article  Google Scholar 

  22. Feng, J. X.; Wu, J. Q.; Tong, Y. X.; Li, G. R. Efficient hydrogen evolution on Cu nanodots-decorated Ni3S2 nanotubes by optimizing atomic hydrogen adsorption and desorption. J. Am. Chem. Soc. 2018, 140, 610–617.

    Article  Google Scholar 

  23. Feng, J. X.; Tong, S. Y.; Tong, Y. X.; Li, G. R. Pt-like hydrogen evolution electrocatalysis on PANI/CoP hybrid nanowires by weakening the shackles of hydrogen ions on the surfaces of catalysts. J. Am. Chem. Soc. 2018, 140, 5118–5126.

    Article  Google Scholar 

  24. Yang, F. L.; Chen, Y. T.; Cheng, G. Z.; Chen, S. L.; Luo, W. Ultrathin nitrogen-doped carbon coated with CoP for efficient hydrogen evolution. ACS Catal. 2017, 7, 3824–3831.

    Article  Google Scholar 

  25. Tian, J. Q.; Liu, Q.; Asiri, A. M.; Sun, X. P. Self-supported nanoporous cobalt phosphide nanowire arrays: An efficient 3D hydrogen-evolving cathode over the wide range of pH 0–14. J. Am. Chem. Soc. 2014, 136, 7587–7590.

    Article  Google Scholar 

  26. Liu, Q.; Tian, J. Q.; Cui, W.; Jiang, P.; Cheng, N. Y.; Asiri, A. M.; Sun, X. P. Carbon nanotubes decorated with CoP nanocrystals: A highly active non-noble-metal nanohybrid electrocatalyst for hydrogen evolution. Angew. Chem., Int. Ed. 2014, 53, 6710–6714.

    Article  Google Scholar 

  27. Yang, Y.; Fei, H. L.; Ruan, G. D.; Tour, J. M. Porous cobalt-based thin film as a bifunctional catalyst for hydrogen generation and oxygen generation. Adv. Mater. 2015, 27, 3175–3180.

    Article  Google Scholar 

  28. Yang, X. L.; Lu, A. Y.; Zhu, Y. H.; Hedhili, M. N.; Min, S. X.; Huang, K. W.; Han, Y.; Li, L. J. CoP nanosheet assembly grown on carbon cloth: A highly efficient electrocatalyst for hydrogen generation. Nano Energy 2015, 15, 634–641.

    Article  Google Scholar 

  29. Zhang, X. Y.; Gu, W. L.; Wang, E. K. Self-supported ternary Co0.5Mn0.5P/carbon cloth (CC) as a high-performance hydrogen evolution electrocatalyst. Nano Res. 2017, 10, 1001–1009.

    Article  Google Scholar 

  30. Zhang, X. Y.; Gu, W. L.; Wang, E. K. Wire-on-flake heterostructured ternary Co0.5Ni0.5P/CC: An efficient hydrogen evolution electrocatalyst. J. Mater. Chem. A 2017, 5, 982–987.

    Article  Google Scholar 

  31. Li, J. Y.; Yan, M.; Zhou, X. M.; Huang, Z. Q.; Xia, Z. M.; Chang, C. R.; Ma, Y. Y.; Qu, Y. Q. Mechanistic insights on ternary Ni2–xCoxP for hydrogen evolution and their hybrids with graphene as highly efficient and robust catalysts for overall water splitting. Adv. Funct. Mater. 2016, 26, 6785–6796.

    Article  Google Scholar 

  32. Tang, C.; Gan, L. F.; Zhang, R.; Lu, W. B.; Jiang, X. E; Asiri, A. M.; Sun, X. P.; Wang, J.; Chen, L. Ternary FexCo1–xP nanowire array as a robust hydrogen evolution reaction electrocatalyst with Pt-like activity: Experimental and theoretical insight. Nano Lett. 2016, 16, 6617–6621.

    Article  Google Scholar 

  33. Liu, T. T.; Liu, D. N.; Qu, F. L.; Wang, D. X.; Zhang, L.; Ge, R. X.; Hao, S.; Ma, Y. J.; Du, G.; Asiri, A. M. et al. Enhanced electrocatalysis for energyefficient hydrogen production over CoP catalyst with nonelectroactive Zn as a promoter. Adv. Energy Mater. 2017, 7, 1700020.

    Article  Google Scholar 

  34. Gu, W. L.; Gan, L. F.; Zhang, X. Y.; Wang, E. K.; Wang, J. Theoretical designing and experimental fabricating unique quadruple multimetallic phosphides with remarkable hydrogen evolution performance. Nano Energy 2017, 34, 421–427.

    Article  Google Scholar 

  35. Jiang, P.; Liu, Q.; Ge, C. J.; Cui, W.; Pu, Z. H.; Asiribc, A. M.; Sun, X. P. CoP nanostructures with different morphologies: Synthesis, characterization and a study of their electrocatalytic performance toward the hydrogen evolution reaction. J. Mater. Chem. A, 2014, 2, 14634–14640.

    Article  Google Scholar 

  36. Zhang, H. G.; Hwang, S.; Wang, M. Y.; Feng, Z. X.; Karakalos, S.; Luo, L. L.; Qiao, Z.; Xie, X. H.; Wang, C. M.; Su, D. et al. Single atomic iron catalysts for oxygen reduction in acidic media: Particle size control and thermal activation. J. Am. Chem. Soc. 2017, 139, 14143–14149.

    Article  Google Scholar 

  37. Chen, Y. Z.; Wang, C. M.; Wu, Z. Y.; Xiong, Y. J.; Xu, Q.; Yu, S. H.; Jiang, H. L. From bimetallic metal-organic framework to porous carbon: High surface area and multicomponent active dopants for excellent electrocatalysis. Adv. Mater. 2015, 27, 5010–5016.

    Article  Google Scholar 

  38. Deng, J.; Ren, P. J.; Deng, D. H.; Bao, X. H. Enhanced electron penetration through an ultrathin graphene layer for highly efficient catalysis of the hydrogen evolution reaction. Angew. Chem., Int. Ed. 2015, 54, 2100–2104.

    Article  Google Scholar 

  39. Yang, Y.; Lun, Z. Y.; Xia, G. L.; Zheng, F. C.; He, M. N.; Chen, Q. W. Non-precious alloy encapsulated in nitrogen-doped graphene layers derived from MOFs as an active and durable hydrogen evolution reaction catalyst. Energy Environ. Sci. 2015, 8, 3563–3571.

    Article  Google Scholar 

  40. Zhang, Z.; Hao, J. H.; Yang, W. S.; Tang, J. L. Defect-rich CoP/ nitrogendoped carbon composites derived from a metal-organic framework: High-performance electrocatalysts for the hydrogen evolution reaction. ChemCatChem 2015, 7, 1920–1925.

    Article  Google Scholar 

  41. Huang, Y.; Gong, Q. F.; Song, X. N.; Feng, K.; Nie, K. Q.; Zhao, F. P.; Wang, Y. Y.; Zeng, M.; Zhong, J.; Li, Y. G. Mo2C nanoparticles dispersed on hierarchical carbon microflowers for efficient electrocatalytic hydrogen evolution. ACS Nano 2016, 10, 11337–11343.

    Article  Google Scholar 

  42. Yang, W. X.; Liu, X. J.; Yue, X. Y.; Jia, J. B.; Guo, S. J. Bamboo-like carbon nanotube/Fe3C nanoparticle hybrids and their highly efficient catalysis for oxygen reduction. J. Am. Chem. Soc. 2015, 137, 1436–1439.

    Article  Google Scholar 

  43. Conway, B. E.; Tilak, B. V. Interfacial processes involving electrocatalytic evolution and oxidation of H2, and the role of chemisorbed H. Electrochim. Acta 2002, 47, 3571–3594.

    Article  Google Scholar 

  44. Pentland, N.; Bockris, J. O.; Sheldon, E. Hydrogen evolution reaction on copper, gold, molybdenum, palladium, rhodium, and iron. J. Electrochem. Soc. 1957, 104, 182–194.

    Article  Google Scholar 

  45. Peng, Z.; Jia, D. S.; Al-Enizi, A. M.; Elzatahry, A. A.; Zheng, G. F. From water oxidation to reduction: Homologous Ni-Co based nanowires as complementary water splitting electrocatalysts. Adv. Energy Mater. 2015, 5, 1402031.

    Article  Google Scholar 

  46. Xu, J.; Cui, J. B.; Guo, C.; Zhao, Z. P.; Jiang, R.; Xu, S. Y.; Zhuang, Z. B.; Huang, Y.; Wang, L. Y.; Li, Y. D. Ultrasmall Cu7S4@MoS2 hetero-nanoframes with abundant active edge sites for ultrahigh-performance hydrogen evolution. Angew. Chem., Int. Ed. 2016, 55, 6502–6505.

    Article  Google Scholar 

  47. Zhang, H. B.; Ma, Z. J.; Duan, J. J.; Liu, H. M.; Liu, G. G.; Wang, T.; Chang, K.; Li, M.; Shi, L.; Meng, X. G. et al. Active sites implanted carbon cages in core-shell architecture: Highly active and durable electrocatalyst for hydrogen evolution reaction. ACS Nano 2016, 10, 684–694.

    Article  Google Scholar 

  48. Gong, Q. F.; Cheng, L.; Liu, C. H.; Zhang, M.; Feng, Q. L.; Ye, H. L.; Zeng, M.; Xie, L. M.; Liu, Z.; Li, Y. G. Ultrathin MoS2(1–x)Se2x alloy nanoflakes for electrocatalytic hydrogen evolution reaction. ACS Catal. 2015, 5, 2213–2219.

    Article  Google Scholar 

  49. Gao, X. H.; Zhang, H. X.; Li, Q. G.; Yu, X. G.; Hong, Z. L.; Zhang, X. W.; Liang, C. D.; Lin, Z. Hierarchical NiCo2O4 hollow microcuboids as bifunctional electrocatalysts for overall water-splitting. Angew. Chem., Int. Ed. 2016, 55, 6290–6294.

    Article  Google Scholar 

  50. Wang, J.; Zhong, H. X.; Wang, Z. L.; Meng, F. L.; Zhang, X. B. Integrated three-dimensional carbon paper/carbon tubes/cobalt-sulfide sheets as an efficient electrode for overall water splitting. ACS Nano 2016, 10, 2342–2348.

    Article  Google Scholar 

  51. You, B.; Jiang, N.; Sheng, M. L.; Gul, S.; Yano, J.; Sun, Y. J. High-performance overall water splitting electrocatalysts derived from cobalt-based metalorganic frameworks. Chem. Mater. 2015, 27, 7636–7642.

    Article  Google Scholar 

Download references

Acknowledgments

Support from the National Natural Science Foundation of China (No. 21427811), the National Key Research and Development Program of China (No. 2016YFA0203200) and Youth innovation promotion Association CAS (No. 2016208).

Author information

Authors and Affiliations

  1. State Key Laboratory of Electroanalytical Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun, 130022, China

    Wenling Gu, Liuyong Hu, Changshuai Shang, Jing Li & Erkang Wang

  2. University of Chinese Academy of Sciences, Beijing, 100049, China

    Wenling Gu, Liuyong Hu & Changshuai Shang

Authors
  1. Wenling Gu
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Liuyong Hu
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Changshuai Shang
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Jing Li
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Erkang Wang
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding authors

Correspondence to Jing Li or Erkang Wang.

Electronic supplementary material

12274_2018_2201_MOESM1_ESM.pdf

Enhancement of the hydrogen evolution performance by finely tuning the morphology of Co-based catalyst without changing chemical composition

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Gu, W., Hu, L., Shang, C. et al. Enhancement of the hydrogen evolution performance by finely tuning the morphology of Co-based catalyst without changing chemical composition. Nano Res. 12, 191–196 (2019). https://doi.org/10.1007/s12274-018-2201-y

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s12274-018-2201-y

Keywords

Search

Navigation